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WO1996027586A1 - Dispersions de peroxyde organique de diacyle solide - Google Patents

Dispersions de peroxyde organique de diacyle solide Download PDF

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Publication number
WO1996027586A1
WO1996027586A1 PCT/EP1996/000932 EP9600932W WO9627586A1 WO 1996027586 A1 WO1996027586 A1 WO 1996027586A1 EP 9600932 W EP9600932 W EP 9600932W WO 9627586 A1 WO9627586 A1 WO 9627586A1
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WIPO (PCT)
Prior art keywords
peroxide
weight
mixtures
phlegmatizing
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1996/000932
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English (en)
Inventor
Bryce Milleville
Borys F. Schafran
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Akzo Nobel NV
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Akzo Nobel NV
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Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to JP8526606A priority Critical patent/JPH11501624A/ja
Priority to EP96907359A priority patent/EP0813522A1/fr
Priority to MXPA/A/1997/006845A priority patent/MXPA97006845A/xx
Priority to BR9607662A priority patent/BR9607662A/pt
Publication of WO1996027586A1 publication Critical patent/WO1996027586A1/fr
Priority to NO974104A priority patent/NO974104L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C07C407/003—Separation; Purification; Stabilisation; Use of additives
    • C07C407/006—Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical

Definitions

  • the present invention generally relates to solid diacyl organic peroxide dispersions in liquid or paste form having a solid organic peroxide content of 3-60% by weight.
  • Diacyl peroxides are widely used as polymerization initiators, curing agents and bleaching agents. Dry peroxides of this family are, however, hazardous in dry form since they are extremely shock sensitive and flammable. By mixing these peroxides with inert substances which act as desensitizing agents, the peroxides can assume a phlegmatized state which makes the handling of these hazardous materials almost harmless. Paste and liquid formulations also allow for pumping and in some cases, spraying capabilities.
  • Standard organic ester plasticizers such as phthalates, benzoates and dibenzoates, phosphates, citrates, adipates, etc.
  • dispersing and/or de- agglomerating solid diacyl peroxides e.g., dibenzoyl peroxide
  • plasticizers are typically employed in large amounts and allow for the dispersion of solid diacyl peroxide in standard mixing equipment (kneading mixers, planetary mixers, or high speed dispersers) giving smooth uniform dispersions in a reasonable time frame.
  • solid diacyl peroxide can be prepared as a fine particle suspension/dispersion in plasticizer and/or water if the peroxide is (1) preground to a fine particle size ( ⁇ 10-20 microns) or (2) ground in-situ during the mixing phase using a homogenizer type mixer.
  • a liquid or paste dispersion which comprises a diaroyl peroxide, a liquid alkyl ester of benzoic acid in which the alkyl group of the ester has from 8 to 12 carbon atoms, and water from 0.0 to 40% by weight.
  • the ratio of said diaroyl peroxide to the said alkyl benzoate is from 0.3:1 to 7:1.
  • U.S. Patent No. 4,255,277 describes a non-separating catalyst paste comprising a diacyl peroxide; a minor proportion of water; a finely divided calcium carbonate in an amount sufficient to prevent the composition from physically separating into its components.
  • U.S. Patent No. 4,376,218 describes solid organic peroxide compositions (pastes) containing from 50% to below 70% by weight of a solid organic peroxide, such as dibenzoyl peroxide, and a combination of liquid and solid desensitizers, wherein the amount of liquid desensitizer must comprise at least 10% by weight of the composition.
  • a solid organic peroxide such as dibenzoyl peroxide
  • liquid desensitizers include liquid esters of phthalic acid, benzoic acid or phosphoric acid, silicone oil, a liquid chlorinated hydrocarbon and the like.
  • the solid desensitizer can be, for example, a solid ester of phthalic acid, benzoic acid or phosphoric acid, a solid chlorinated hydrocarbon or a salt of a higher fatty acid, and is included in the composition in preferred amounts of less than 20% by weight.
  • U.S. Patent No. 3,723,336 discloses a non-separating composition consisting of 20 to 60 parts of dibenzoyl peroxide or dibenzoyl peroxide having one or more substituents selected from halogen, lower alkyl or lower alkoxy; up to 20 parts of water; a hydrophobic reaction product of a pyrogenic silica with dimethyl dichlorosilane in an amount sufficient to prevent the composition from physically separating into its components, the composition having at least 2 parts and up to 6 parts silica; and the remainder being a chemically inert plasticizer.
  • a free radical-generating organic peroxide comprising: a free radical-generating organic peroxide; said peroxide being solid at room temperature; up to 20 parts of water; a hydrophobic lower alkyl substituted silica which is the reaction product of a pyrogenic silica with a lower dialkyl dichlorosilane in an amount sufficient to prevent the composition from physically separating into its components, the composition having at least 2 parts and up to 6 parts of the reaction product; and the remainder being a liquid substance which is inert to the organic peroxide and in which the peroxide is substantially insoluble, said liquid substance being composed of one or more compounds selected from the group consisting of plasticizers and organic solvents.
  • U.S. Patent No. 3,538,011 discloses a stabilized composition with reduced explosiveness consisting of an organic peroxide, 20-60% by weight of a plasticizer which contains at least 70% by weight of chlorine, ethylene glycol dibenzoate, triethylene glycol dibenzoate, trimethylene glycol dibenzoate and mixtures thereof .
  • U.S. Patent No. 4,039,475 describes pumpable highly concentrated aqueous suspensions of organic peroxides containing (a) nonionic emulsifiers having a maximum HLB value of 12.5 and (b) nonionic emulsifiers having a minimum HLB value of 12.5 or anionic emulsifiers.
  • U.S. Patent No. 4,917,816 describes organic peroxide compositions containing (a) from 35-70% by weight solid dibenzoyl peroxide particles having a particle size of 10 microns or less, (b) water (c) a compound that produces an ionic region about the peroxide particles in the dispersion, is inert as to the peroxide, and is at least water dispersible wherein said compound is selected from the group consisting of finely divided fumed silica, a sodium salt of a condensed naphthalene sulfonic acid and a sodium salt of a polymerized carboxylic acid: (d) a defoamer; and (e) a water soluble acidic inorganic salt which is inert as to the peroxide, increases the viscosity of the dispersion, retains water of hydration upon dry down of the dispersion and possesses fire retardant properties.
  • compositions employ large amounts of plasticizers to disperse the solid peroxide based on their ability to partially dissolve the peroxide without affecting the chemical and thermal stability of the peroxide.
  • a system has now been discovered whereby a highly stable dispersion/suspension of solid diacyl organic peroxides can be prepared with the minimal use of plasticizers.
  • the formulation of the present invention has increased thermal stability due to reduced solvation of the peroxide and allows the use of secondary phlegmatizing vehicles having no or minimal dispersing/solvating ability for the peroxide without the necessity of particle size reduction equipment. Further, in products comprising dibenzoyl peroxide the amount of free benzene in the final product over time caused by the slow decomposition of dibenzoyl peroxide is substantially reduced which, in turn, is related to the superior thermal stability of the pastes/dispersions of the present invention.
  • the present invention generally relates to solid diacyl organic peroxide formulations in liquid or paste form.
  • the formulations generally comprise solid diacyl organic peroxide, minimal amounts of a dispersing plasticizer, a phlegmatizing vehicle having a no or minimal solid organic peroxide solubility, and optionally, surfactants, thixotropic agents, mixtures thereof and the like.
  • the present invention relates to solid diacyl organic peroxide formulations in a liquid or paste form.
  • the formulations of the present invention generally comprise solid diacyl organic peroxide, minimal amounts of a dispersing plasticizer, a phlegmatizing vehicle having minimal or no solid organic peroxide solubility, and optionally, surfactants, thixotropic agents, mixtures thereof and the like.
  • the present invention allows one to employ small amounts of dispersing plasticizers to facilitate the breakdown of diacyl peroxide into primary particles, supplemented by the incorporation of a secondary liquid phlegmatizing vehicle having minimal or no peroxide solubility. Previously, said dispersions could not be accomplished with known mixing equipment/processes without secondary particle size reduction.
  • the formulations of the present invention are superior to known formulations which contain only large amounts of dispersing plasticizer in that they (i) have increased thermal stability/ safety properties due to the reduced solvation of the diacyl peroxide; (ii) allow the use of liquid phlegmatizing vehicles having no or minimal dispersing/solvating ability for the peroxide without the necessity of employing particle size reduction equipment; (iii) in compositions based on dibenzoyl peroxide, they have substantially reduced amount of free benzene in the final product over time caused by the decomposition of the peroxide primarily by the dispersing plasticizer; and, of course, they are commercially cheaper because less dispersing plasticizer is employed and because the need for expensive particle size reduction equipment is eliminated.
  • Diacyl peroxides useful in the present invention are of the general formula:
  • R is an alkyl, cycloalkyl, aralkyl aryl or heterocyclic radical.
  • preferred solid diacyl peroxides include but are not limited to di- (p-chlorobenzoyl) peroxide, di- (2,4-dichlorobenzoyl)peroxide, acetyl benzoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, benzoyl (2,4-dichloro benzoyl) peroxide, bis (3-dibutyl phosphino-2-methyl propanoyl) peroxide, bis (2, 6-dimethyl benzoyl) peroxide, bis (3,4-dimethoxy benzoyl) peroxide, bis (3, 3-dimethyl butanoyl) peroxide, bis (2-methyl benzoyl) peroxide, dicyclohexyl carbonyl peroxide, didecanoyl peroxide, difuroy
  • the most preferred diacyl peroxide is dibenzoyl peroxide.
  • the dispersions of the present invention generally contain from about 3% to about 60% by weight diacyl peroxide. More preferably, dispersions according to the present invention contain from about 25% to about 60% by weight diacyl peroxide. In a most preferred embodiment, the dispersions contain from about 38% to about 57% by weight diacyl peroxide.
  • the dispersing plasticizer is preferably an organic medium capable of partially dissolving/de-agglomerating diacyl peroxide particles into an average particle size of from about 5-30 urn when added in the lowest possible amount.
  • Preferred dispersing plasticizers are mono- and di- organic acid esters having a diacyl peroxide solubility of from about 4-10%.
  • Suitable dispersing plasticizers with diacyl peroxide solubility of from 4-10% include but are not limited to acetates, adipates, benzoates, citrates, hexanoates, lactates, maleates, phosphates, phthalates, sebacates, tallates and soy derivatives.
  • dispersing plasticizers include but are not limited to
  • 2-ethylhexyl diphenyl phosphate isodecyl diphenyl phosphate, tributylethyl phosphate, tributyl phosphate, alkyl benzyl phthalates, dicyclohexyl phthalate, diphenyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, diisooctyl phthalate, polygylcol phthalate dibutyl phthalate, di-1-nonyl phthalate, di-isodecyl phthalate, dibutyl sebacate, isooctyl tallate, epoxidized soy bean oil, and the like.
  • dispersing plasticizers include dipropylene glycol dibenzoate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, alkyl benzyl phthalates, diisobutyl phthalate and alkyl benzoates wherein the alkyl chain has from eight (8) to twelve (12) carbon atoms.
  • the most preferred benzoate ester is isodecyl benzoate.
  • the ratio of diacyl peroxide :alkyl benzoate be greater than about 7:1, and more preferably, within the range of 7.1:1 to about 12:1.
  • the phlegmatizing vehicle is preferably water and/or an organic medium with minimal or no solvating/dispersing ability for the diacyl peroxide and its primary purpose is to act as a diluent for the peroxide/dispersing plasticizer intermediate.
  • dioctyl terephthalate are usefully employed as phlegmatizing vehicles.
  • the aliphatic hydrocarbons are preferably normal or iso-paraffinic hydrocarbons such as C 15 n-paraffins, while light napthenic hydrotreated distillates are acceptable aromatic hydrocarbons. Generally, however, most hydrocarbons with a flash point of greater than about 100°F, a melting point of less than about 68°F and a boiling point of greater than about 212°F are employable in the present invention. Examples of such hydrocarbons include Jayflex ® 210 and Jayflex ® 215 sold by Exxon Corporation.
  • the dispersion of the present invention also optionally contains surfactants and/or thixotropic agents.
  • surfactants Conventional and polymeric nonionic and anionic surfactants can be employed to provide physical stability to the formulation, whether a dispersion, emulsion or suspension.
  • examples of some preferred surfactants include polyethylene glycol mono- and di-esters, polyoxyethylene sorbitan mono- and tri-esters, polyoxyethylene-polyoxyproplyene copolymers, sorbitan mono- and tri-esters, polymeric fatty acid esters sold under the trademark Hypermer by ICI .
  • Hypermer ® B239 polyhydroxy fatty ICI acid-polyethylene glycol block copolymer
  • the amount of surfactant or mixture of surfactants employed is typically in the range of about 0-10% by weight of the dispersion.
  • Thixotropic agents are employed in order to provide the desired rheological properties to the formulation including viscosity, anti-settling and thixotropy. Selection is also dependent upon chemical stability of the final formulation.
  • Conventional and treated acrylic polymer, organoclay, polysaccharides such as cellulose, polyvinyl alcohol, precipitated and fumed silica, silicates, and water soluble natural gums are claimed, with their use being dependent upon the other ingredients of the formulation. Particularly good results have been obtained with the following amorphous hydrophilic and hydrophobic fumed silicas
  • Aerosil R972 Dimethyldichlorosilane, Degussa Corp. R974 or R976 silica reaction product
  • Thixotropic agents or mixtures of thixotropic agents are typically employed in amounts ranging from about 0-10% by weight of the dispersion.
  • the dispersions of the present invention generally contain dispersing plasticizer as a ratio amount based on the amount of diacyl peroxide present. While this ratio varies greatly based on the wt% diacyl peroxide contained in the dispersion and on whether the dispersion is in liquid or paste form, the amount of plasticizer required in the present invention is certainly much less than was otherwise thought possible.
  • the ratio of diacyl peroxidedispersing plasticizer for paste formulations is from about 3.4:1 to about 12:1, more preferably, from about 7.1:1 to about 12:1, and still more preferably, from about 7.3:1 to about 11:1.
  • the typical diacyl peroxide:dispersing plasticizer ratio is from about 3.4:1 to about 12:1, more preferably, about 5 : 1 to about 12:1, and still more preferably, from 7.1:1 to about 12:1.
  • the ratio of diacyl peroxide: alkyl benzoate be greater than about 7:1, and more preferably, within the range of 7.1:1 to about 12:1 to 7.3:1 to 11:1.
  • the balance of the dispersion formulation comprises phlegmatizing vehicle, surfactant and thixotropic agent .
  • the thermal stability of such dispersions can be greatly enhanced if the phlegmatizing vehicle comprises water, and from about 10% by weight to about 90% by weight of at least one additional phlegmatizing vehicle selected from: aliphatic hydrocarbons, aromatic hydrocarbons, azelates, adipates, oleates and phthalates.
  • the aliphatic hydrocarbons such as C 15 n-paraffins, aromatic hydrocarbons light napthenic hydrotreated distillates are preferred and generally provide the greatest improvement in thermal stability.
  • the invention contemplates a stabilized dispersion in paste form which comprises 40-60% by weight solid diacyl organic peroxide; 3-18% by weight dispersing plasticizer having a solid organic peroxide solubility of about 4-10%; 2%- 57% by weight phlegmatizing vehicle having minimal or no solid organic peroxide solubility; and optionally, at least one surfactant and at least one thixotropic/anti-settling agent.
  • the dispersion of the present invention comprises 48%-52% by weight solid diacyl organic peroxide; 4%-8% by weight dispersing plasticizer having a solid organic peroxide solubility of about 4-10%; 20%-48% phlegmatizing vehicle having minimal or no peroxide solubility; 0-10% by weight of at least one surfactant, and 0-10% of at least one thixotropic agent.
  • BPO dibenzoyl peroxide
  • the invention contemplates a stabilized dispersion in paste form which comprises 53-57% by weight diacyl peroxide; 4-8% by weight dispersing plasticizer; 15-43% by weight phlegmatizing vehicle having minimal or no peroxide solubility; 0-10% surfactant and 0-10% thixotropic agent.
  • a preferred example of such a formulation would be a 55% BPO paste which comprises from 53%- 57% by weight BPO, from 4-8% by weight isodecyl benzoate wherein the BPO: isodecyl benzoate ratio is greater than about 7.1:1, 0-10% of at least one surfactant, 0-10% of at least one thixotropic agent, and the remainder, phlegmatizing vehicle.
  • the invention contemplates a stabilized dispersion in liquid form which comprises 30-50% by weight diacyl peroxide; 2-15% by weight dispersing plasticizer; 15-68% by weight phlegmatizing vehicle having minimal or no peroxide solubility; and optionally, at least one surfactant and at least one thixotropic agent .
  • the invention contemplates a stabilized dispersion in liquid form which comprises 30-50% by weight diacyl peroxide; 2-10% by weight dispersing plasticizer; 20-68% by weight phlegmatizing vehicle having minimal or no peroxide solubility; and optionally, at least one surfactant and at least one thixotropic agent, with the requirement that said phlegmatizing vehicle comprises water, and from about 10% to about 90% of aliphatic hydrocarbon, aromatic hydrocarbon, and mixtures thereof.
  • the invention contemplates a stabilized dispersion in liquid form which comprises 38-42% by weight diacyl peroxide; 3-6% by weight dispersing plasticizer; 29-59% by weight phlegmatizing vehicle having minimal or no peroxide solubility; and optionally, 0-10% of at least one surfactant and 0-10% of at least one thixotropic agent.
  • a preferred example of such a formulation would be a 40% BPO dispersion (liquid) which comprises from 38%-42% by weight BPO, from 3-6% by weight alkyl benzyl phthalate, 0-10% of at least one surfactant, 0-10% of at least one thixotropic agent, and the remainder, phlegmatizing vehicle.
  • the present invention contemplates a non-aqueous dispersion which comprises diacyl peroxide, at least one dispersing plasticizer, at least one phlegmatizing vehicle (as defined above, excluding water) , and optionally, at least one surfactant, and at least one thixotropic agent.
  • the dispersions of the present invention are prepared using mixing equipment generally known in the art.
  • dispersing plasticizer is added to wet peroxide and mixed to prepare a fine-particle sized 60-65% intermediate.
  • Phlegmatizing vehicle is then added to produce a peroxide concentration of from about 20-55%.
  • Surfactant (s) and thixotropic agent (s) are added during the process at such time to produce the desired characteristics of the final formulation. No milling or other specialized equipment is necessary to produce these formulations.
  • Example 1 55% Dibenzoyl peroxide (BPO) Paste
  • BPO Dibenzoyl peroxide
  • the mixer was charged with BPO (BPO 75% in water) , benzoate, water, and zinc stearate.
  • a preproduct was formed after about 30 minutes of mixing.
  • Nonionic surfactant (Tergitol XD) was then added to emulsify the oil into the water phase. After about 30 minutes, a smooth, short, uniform paste of the following composition was produced.
  • Comparative Example 2 generally describes a generic BPO paste containing large amounts of butyl benzyl phthalate as a solvating plasticizer in accordance with the prior art.
  • Comparative Example 3 is a sample of Benox ® B55-108, a commercial paste obtained from the Norac Company.
  • Zinc stearate 1 and the remainder, surfactant and water are zinc and zinc.
  • Diacyl peroxides will decompose when they are subjected to a sufficiently high temperature level.
  • the rate of decomposition depends on both the components and the temperature. The effects can be calculated using r order kinetics and the Arrhenius equation. The rate of decomposition is proportional to the heat production measured with differential scanninq calorimetry (DSC) .
  • the temperature at which a heat production of 100 W/kg is reached was used as the isothermal temperature.
  • This value is generally 80°C for dibenzoyl peroxide paste and liquid formulations, and is obtained from dynamic scans at 2°C/min (50 mg sample, medium pressure sample pan) .
  • Table 1 shows the isothermal DSC results of a 55% BPO paste prepared in accordance with the present invention, i.e., that of Example 1, versus the 55% BPO pastes of Comparative Examples 2 and 3.
  • Comparative Example 2 50 50 50 50 51 8.6 Comparative Example 3 24 26 29 32 34 30.3 Isothermal data was also measured at 85°C and the very long time-to-peak interval for the formulation of the present invention is clearly indicative of a higher thermal stability as compared to the formulations of the prior art.
  • the present invention also experiences reduced benzene formation due to a decrease in the amount of dispersing plasticizer employed, and the greater thermal stability of the formulations.
  • the rate of benzene formation was measured for two compositions;
  • the Composition of Example A was prepared in accordance with the present invention and has a peroxide:plasticizer ratio of 11:1, while that of Comparative Example B possesses a peroxide :plasticizer ratio of 3.67:1.
  • the rate of benzene formation was measured by equilibrating samples in a Dani headspace instrument followed by analysis of the headspace via GC/MS. Benzene D6 was used as an internal standard.
  • Headspace conditions were: 70°C bath temperature, 100°C manifold temperature, pressurized from 0-40 seconds, vented from 41-140 seconds, injected from 120-140 seconds at 2 bar, 1.8 bar on transfer line.
  • GC/MS conditions were: 25 m x 0.25 mm 1 urn DB-5 50°C to 80°C at 10°C/min, full scan, 15 psi on column, split flow approximately 15 ml/min.
  • Example A containing 67% less isodecyl benzoate as dispersing plasticizer resulted in a 78% decrease in benzene formation as compared with Comparative Example B, a formulation common to the prior art .
  • Example 4 40% Dibenzoyl (BPO) Dispersion (Liquid) BPO (75% in water) , benzoate, and water were added to the mixer and blended for 30 minutes to produce a 65% intermediate product. Hydrocarbon (Jayflex ® 215) and surfactant (Hypermer ® B239) were then added and mixed for 10 minutes to create a dispersion of BPO in a water-in-oil emulsion. Silica (Aerosile ® R974) was then added and mixed for 10 minutes, creating a thixotropic, uniform liquid.
  • BPO Dibenzoyl
  • BPO (75% in water) and C 7 -C 9 alkyl benzyl phthalate plasticizer (Santicizer ® 261 purchased from Monsanto) were added to the mixer and blended for 30 minutes to produce a 65% intermediate product.
  • Hydrocarbon (Jayflex ® 215) and surfactant (Hyper er ® 2296/Tween ® 80) were then added and mixed for 10 minutes to create a dispersion of BPO in a water-in-oil emulsion.
  • Fumed hydrophobic silica (Cabosil TS530) was thereafter added and mixed for 10 minutes, creating a thixotropic, uniform liquid having the following composition.
  • Component Weight % (Cabosil TS530)
  • Benzoate and surfactant (Hypermer B239) were added to the mixer and blended for 10 minutes.
  • Silica (Aerosilv4, 22 R974) was then added and mixed for an additional 10 minutes creating a thixotropic liquid.
  • BPO (75% in water) was added last and mixed for 20 minutes to produce a BPO dispersion in a water-in-oil emulsion having the following composition.
  • Table 2 shows the isothermal DSC results for two 40% BPO liquid dispersions according to the present invention (Example 4 and 5) verses that of a typical formulation of the prior art (Comparative Example 6) .
  • Example 4 clearly shows that when the liquid dispersions of the present invention employ phlegmatizing vehicles comprising water and from 10-90% aliphatic or aromatic hydrocarbon, the thermal stability of the dispersion increases dramatically.

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Abstract

La présente invention concerne, de manière générale, des compositions de peroxyde organique de diacyle solide, se présentant sous forme liquide ou de pâte et ayant une stabilité thermique améliorée. Ces compositions contiennent, de manière générale, du peroxyde organique de diacyle solide, un plastifiant de dispersion ayant une solubilité envers le peroxyde organique solide variant environ entre 3 et 10 %, un véhicule d'agent flegmatisant ayant une solubilité envers le peroxyde organique solide minimale ou nulle, ainsi que d'éventuels ingrédients tel que des agents tensioactifs, des agents thixotropiques, des mélanges de ces agents ou des produits similaires.
PCT/EP1996/000932 1995-03-07 1996-03-04 Dispersions de peroxyde organique de diacyle solide Ceased WO1996027586A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP8526606A JPH11501624A (ja) 1995-03-07 1996-03-04 固体ジアシル有機パーオキシドの分散物
EP96907359A EP0813522A1 (fr) 1995-03-07 1996-03-04 Dispersions de peroxyde organique de diacyle solide
MXPA/A/1997/006845A MXPA97006845A (en) 1995-03-07 1996-03-04 Organic peroxide dispersions of diacilo sol
BR9607662A BR9607662A (pt) 1995-03-07 1996-03-04 Dispersão em forma de pasta e líquida não aquosa estabilizada
NO974104A NO974104L (no) 1995-03-07 1997-09-05 Faste diacyl-organiske peroksyd-dispersjoner

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/400,146 US5690856A (en) 1995-03-07 1995-03-07 Solid diacyl organic peroxide dispersions
US08/400,146 1995-03-07

Publications (1)

Publication Number Publication Date
WO1996027586A1 true WO1996027586A1 (fr) 1996-09-12

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PCT/EP1996/000932 Ceased WO1996027586A1 (fr) 1995-03-07 1996-03-04 Dispersions de peroxyde organique de diacyle solide

Country Status (10)

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US (1) US5690856A (fr)
EP (1) EP0813522A1 (fr)
JP (1) JPH11501624A (fr)
KR (1) KR19980702865A (fr)
CN (1) CN1075493C (fr)
BR (1) BR9607662A (fr)
CA (1) CA2214785A1 (fr)
NO (1) NO974104L (fr)
TW (1) TW382026B (fr)
WO (1) WO1996027586A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032845A1 (fr) * 1996-03-05 1997-09-12 Akzo Nobel N.V. Reduction de la formation de benzene dans des formulations de dibenzoyl peroxyde
EP2508507A1 (fr) * 2011-04-07 2012-10-10 LANXESS Deutschland GmbH Composés acylés du glycerol et leur utilisation en tant que stabilisateurs ou flegmatisants de peroxydes et formulations contenant des peroxydes
US9085649B2 (en) 2009-04-03 2015-07-21 Akzo Nobel Chemicals International B.V. Aqueous solid diacyl peroxide suspension
EP3728187B1 (fr) 2017-12-19 2022-06-22 Nouryon Chemicals International B.V. Procédé de préparation d'une formulation de peroxyde organique sous forme de poudre
FR3138434A1 (fr) * 2022-08-01 2024-02-02 Arkema France Procédé pour la préparation d’une composition sous forme de poudre comprenant au moins un peroxyde organique solide

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* Cited by examiner, † Cited by third party
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CA2437720C (fr) * 2001-02-14 2007-12-18 The Procter & Gamble Company Compositions parfumees pour lave-vaisselle renfermant un agent de blanchiment au peroxyde de diacyle
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NO974104L (no) 1997-11-04
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BR9607662A (pt) 1998-06-16
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JPH11501624A (ja) 1999-02-09
MX9706845A (es) 1997-11-29
KR19980702865A (ko) 1998-08-05
NO974104D0 (no) 1997-09-05
CN1075493C (zh) 2001-11-28
US5690856A (en) 1997-11-25
CN1181068A (zh) 1998-05-06

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